US4066698A - Process for the manufacture of organic hydrazines - Google Patents

Process for the manufacture of organic hydrazines Download PDF

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Publication number
US4066698A
US4066698A US05/606,108 US60610875A US4066698A US 4066698 A US4066698 A US 4066698A US 60610875 A US60610875 A US 60610875A US 4066698 A US4066698 A US 4066698A
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chloramine
amine
organic
liquid phase
group
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US05/606,108
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Hermann Clasen
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes

Definitions

  • This invention relates to an improved process for the manufacture of organic hydrazines.
  • organic hydrazines for example methylhydrazine, phenylhydrazine and the like, by reacting chloramines with primary and secondary aliphatic and cycloaliphatic amines or aniline in the liquid phase under practically anhydrous conditions (cf. Angewandte Chemie 72, (1960), pages 129-130, German Pat. No. 964,865).
  • the aliphatic hydrazines are obtained in a good yield, but in can be gathered from the original literature cited in the above references that the concentrations of organic hydrazine are very low (0.2% by weight only). Due to the low concentration this mode of preparation is very uneconomical.
  • the problem is solved by intensely agitating or finely dividing the liquid phase containing the primary or secondary amine during the introduction of the chloramine.
  • the present invention therefore provides a process for the manufacture of organic substituted hydrazines by introducing unsubstituted chloramine or a chloramine substituted by one or two alkyl groups into a liquid substantially anhydrous phase consisting of a liquid primary or secondary amine or a primary or secondary amine dissolved in an inert solvent, which comprises intensely agitating or finely dividing the liquid phase during the introduction of the chloramine.
  • Suitable chloramines in the process of the invention are, besides the unsubstituted chloramine ClNH 2 itself, chloramines carrying one or two alkyl groups as substituents, for example methyl chloramine, n-propyl chloramine, i-butyl chloramine, diethyl chloramine, which can be prepared in known manner, for example as described in "Allgemeine und Praktician Chemie” 21 (1970), pages 123-124; “Chemikerzeitung/Chemische Apparatur” 92 (1968), pages 383 et seq. or U.S. Pat. No. 2,808,439.
  • the chloramines are all obtained in admixture with ammonia or the primary or secondary starting amines used and an inert gas such as nitrogen, optionally also in admixture with finely divided ammonium chloride or the hydrochloride of the starting amine.
  • the chloramine containing gas mixture is introduced into the intensely agitated or finely divided liquid and substantially anhydrous phase consisting of the liquid primary or secondary amine used or of a solution of the said amine in an inert solvent, or it is passed over the liquid phase.
  • Suitable primary and secondary amines are aliphatic, cycloaliphatic, aromatic and araliphatic amines such as, for example, n-butyl amine, n-hexyl amine, cyclohexyl amine, piperidine, piperazine, aniline, diphenyl amine, o-toluidine, o-anisidine, benzidine, and preferably aniline.
  • the amines can be used as such in liquid form or in the form of a solution in an inert solvent such as aliphatic or aromatic hydrocarbons and halohydrocarbons, for example n-hexane, petroleum ether, benzene, toluene, chlorobenzene; ethers such as diethyl ether, dioxane, or tetrahydrofurane.
  • an inert solvent such as aliphatic or aromatic hydrocarbons and halohydrocarbons, for example n-hexane, petroleum ether, benzene, toluene, chlorobenzene; ethers such as diethyl ether, dioxane, or tetrahydrofurane.
  • a solvent is preferred with amines having a high melting point.
  • the water content of the liquid phase should not exceed noticeably about 0.5% by weight since higher water contents diminish the yield of the desired organic hydrazines. If the amines or solvents used are difficult to prepare in anhydrous form known substances, such as glue or gelatin, are added as heavy metal acceptors to counteract the unfavorable influence of water.
  • the chloramine containing gas current may surprisingly have a temperature up to about 300° C, while the temperature of the liquid phase should not exceed substantially 150° C.
  • the temperature to be chosen depends, in the first place, on the boiling points of the amine and of the solvent, if any.
  • the lower temperature limit of the gas current and of the liquid phase is essentially determined by the fact that at too low a temperature the reaction speed is too slow. Hence, an acceptable lower limit is approximately room temperature.
  • the essential characteristic of the present invention is the intense agitation or the fine division of the liquid phase during the introduction of the chloramine or the chloramine containing gas current.
  • the intense agitation is preferably brought about by stirring and/or circulation by pumping and/or vaporization and/or intense shaking of the liquid in a vibration mixer.
  • a Venturi tube is a tube that has flaring ends connected by a constricted middle section forming a throat.
  • the speed of a gaseous or liquid medium flowing through the tube is increased with decreasing pressure and in the enlarged end the original conditions are approximately adjusted again.
  • the chloramine-(containing)-gas current comes into contact with the liquid phase introduced through a nozzle in the constriction of the Venturi tube the liquid phase is especially intensely agitated in this section and finely divided owing to the increased gas speed.
  • the organic hydrazine formed at the surface is rapidly transported into the interior of the droplets.
  • hydrazobenzene N,N'-diphenylhydrazine
  • concentration has to be varied accordingly. The same applies to the reaction with other amines.
  • the reaction mixture is worked up in usual manner as in the case of the known processes without intense agitation or fine division of the liquid phase.
  • the unsubstituted chloramine is reacted with aniline to yield phenylhydrazine
  • the ammonium chloride formed is mechanically separated by filtration, sedimentation or centrifugation and prior to rectification the filtrate is treated with alkali metal or alkali earth metal compounds.
  • the phenyl-hydrazine is separated from the aniline and small amounts of by-products by rectification.
  • the distillation residue always contains small amount of hydrazobenzene which crystallizes on cooling.
  • the yields of phenylhydrazine amounts to more than 70% of the theory, calculated on the reacted aniline.
  • the process according to the invention is even superior to the conventional process for the manufacture of phenylhydrazine according to E. Fischer (reduction of diazotized aniline with sulfite, or it can at least compete therewith.
  • the organic hydrazines prepared by the process of the invention are important intermediates for a number of syntheses, above all of pharmaceutical products.
  • phenylhydrazine is an important starting material, for example for the known reaction with acetoacetic acid esters to produce pyrazolones.
  • the phenylhydrazine need not be separated from the aniline solution.
  • a device suitable to carry out the process of the invention is diagrammatically illustrated by way of example in the accompanying drawing.
  • the device is composed of three essential elements: the chloramine generator 1, the cooling zone 2 and the amine reactor 3.
  • the chloramine generator 1 comprises as essential parts a reaction cell 4 made of nickel and a nozzle 4a also made of nickel through the axial tube 5 of which chlorine is introduced into the reaction cell.
  • Inlet 6 serves to introduce ammonia or the respective amine. Together with chlorine, ammonia and/or the amine an inert diluting gas may be introduced, for example nitrogen.
  • the reaction cell 4 and the chlorine nozzle 4a are heated by oil-fed circulation heating 7 passing hot oil through the jacket of the reaction cell and of the chlorine nozzle.
  • cooling part 2 which comprises a cylindrical vessel 8 with means 9 for the introduction of a cooling medium through inlet 10 and a funnel-shaped bottom part 11.
  • the cooling medium supplied through inlet 10 is deflected on guide ring 12 and flows in the direction of the gas stream leaving the chloramine generator.
  • Cylindrical vessel 8 is preferably surrounded by an insulating jacket 13 made of any known insulating material.
  • the funnel-shaped outlet 11 of cooling section 2 extends below the surface of the liquid phase in amine vessel 3.
  • Pump 14 produces a liquid jet in transverse direction to the point of introduction and pump 15 produces a liquid counter-current to the issuing gas stream.
  • the issuing gas current is further treated in countercurrent flow over a trickling column 16 by a liquid downdraft of pump 15.
  • the off-gas is discharged from trickling column 16 through outlet 17.
  • the chloramine generator heated by circulating oil heating 7 to 320° C was charged, through inlet 5 of chlorine nozzle 4a with 220 N liters Cl 2 per hour (N meaning measured under normal conditions of pressure and temperature) and through inlet 6 with 1.5Nm 3 NH 3 per hour.
  • Nitrogen was used as cooling medium and introduced into cooling section 2 through inlet 10 in an amount of 12 Nm 3 per hour.
  • baffle ring 12 a coaxial nozzle insert, the nitrogen current was deflected, first in upward direction and then downward so that it streamed uniformly and coaxially through the narrow annular slit between baffle ring 12 and the heat-insulated end section of reaction cell 3 into cylindrical vessel 8 of cooling section 2.
  • the nitrogen current surrounded the hot chloramine containing gas current issuing from reaction cell 3.
  • Two rotary pumps 14 and 15 each having a capacity of about 6m 3 per hour and a gas entraining effect ensured a very vigorous agitation of the aniline which was used in total amount of 17.14 kg and contained 0.095% by weight of water.
  • the off-gas leaving outlet 17 of trickling column 16 was substantially free of ammonium chloride and chloramine.
  • ⁇ designates the molar ratio of chloramine (the chloramine content is determined iodometrically in a gas sample taken at the end of cooling vessel 8) to the chlorine consumed.
  • ⁇ designates the molar ratio of the phenylhydrazine (determined iodometrically in the aniline) to the chloramine (determined as described for ⁇ ).
  • ⁇ is the molar ratio of the phenylhydrazine to the consumed aniline.
  • the dispersed ammonium chloride was separated by filtration and the filtrate mixed with 100 g of 30% NaOH.
  • the dissolved NH 3 was driven out by blowing in N 2 under a pressure of 100 mm Hg, benzene, the water-aniline azeotrope and the aniline and then, at a sump temperature of up to 160° C and while further reducing the pressure, the phenylhydrazine were distilled off.
  • the amount of pure phenylhydrazine obtained corresponded to 95% of the iodometrically determined content. Pure hydrazobenzene could be obtained by crystallization from the distillation residue.
  • the o-tolylhydrazine was obtained in the form of a 5.0% solution.
  • the molar ratio of the iodometrically titrated o-tolylhydrazine to the chloramine used ( ⁇ ) was 0.75 and the molar ratio of o-tolylhydrazine to the consumed toluidine ( ⁇ ) was about 0.85%. Both results were better than in the phenylhydrazine preparation according to Example 1 and o-tolylhydrazine content in the reaction solution increased more rapidly.
  • Example 2 The device as used in Example 1 was charged with 21.8 kg of freshly distilled o-anisidine having a water content of 0.12% by weight.
  • the other reaction conditions were as follows:
  • reaction time about 70 minutes
US05/606,108 1974-08-22 1975-08-20 Process for the manufacture of organic hydrazines Expired - Lifetime US4066698A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2440238A DE2440238C3 (de) 1974-08-22 1974-08-22 Verfahren zur Herstellung von organisch substituierter Hydrazine
DT2440238 1974-08-22

Publications (1)

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US4066698A true US4066698A (en) 1978-01-03

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US05/606,108 Expired - Lifetime US4066698A (en) 1974-08-22 1975-08-20 Process for the manufacture of organic hydrazines

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US (1) US4066698A (ja)
JP (1) JPS5143706A (ja)
BE (1) BE832684A (ja)
BG (1) BG26520A3 (ja)
BR (1) BR7505365A (ja)
CA (1) CA1053704A (ja)
CH (1) CH599129A5 (ja)
CS (1) CS196286B2 (ja)
DD (1) DD120873A5 (ja)
DE (1) DE2440238C3 (ja)
FR (1) FR2282423A1 (ja)
GB (1) GB1526272A (ja)
HU (1) HU174007B (ja)
IT (1) IT1041953B (ja)
LU (1) LU73223A1 (ja)
NL (1) NL7509759A (ja)
PL (1) PL102294B1 (ja)
RO (1) RO69805A (ja)
SU (1) SU546277A3 (ja)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248800A (en) * 1979-03-22 1981-02-03 Pennwalt Corporation Manufacture of organic hydrazines
EP0027645A1 (en) * 1979-10-17 1981-04-29 Hans Osborg Process for preparing hydrazines
US4508695A (en) * 1982-04-22 1985-04-02 Hans Osborg Process for preparing hydrazines
US5563296A (en) * 1993-07-15 1996-10-08 Bayer Aktiengesellschaft Continuous process for preparing aromatic amines
US20070249829A1 (en) * 2003-12-17 2007-10-25 Henri Delalu Method for the Synthesis of Exocyclic Derivatives of Cycloalkyl-Hydrazines and Exocyclic Derivatives of Heterocycloalkyl-Hydrazines

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806851A (en) * 1954-03-25 1957-09-17 Univ Ohio State Res Found Substituted hydrazines
US2901511A (en) * 1956-03-22 1959-08-25 Grace W R & Co Substituted hydrazine process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806851A (en) * 1954-03-25 1957-09-17 Univ Ohio State Res Found Substituted hydrazines
US2901511A (en) * 1956-03-22 1959-08-25 Grace W R & Co Substituted hydrazine process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Stroh, "Method der Organischen Chemie", vol. 10, part 2, pp. 30-34, (1967). *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248800A (en) * 1979-03-22 1981-02-03 Pennwalt Corporation Manufacture of organic hydrazines
EP0027645A1 (en) * 1979-10-17 1981-04-29 Hans Osborg Process for preparing hydrazines
US4508695A (en) * 1982-04-22 1985-04-02 Hans Osborg Process for preparing hydrazines
US5563296A (en) * 1993-07-15 1996-10-08 Bayer Aktiengesellschaft Continuous process for preparing aromatic amines
US20070249829A1 (en) * 2003-12-17 2007-10-25 Henri Delalu Method for the Synthesis of Exocyclic Derivatives of Cycloalkyl-Hydrazines and Exocyclic Derivatives of Heterocycloalkyl-Hydrazines
US7879999B2 (en) * 2003-12-17 2011-02-01 Isochem Method for the synthesis of exocyclic derivatives of cycloalkyl-hydrazines and exocyclic derivatives of heterocycloalkyl-hydrazines

Also Published As

Publication number Publication date
DE2440238A1 (de) 1976-03-04
DE2440238B2 (de) 1980-10-09
DE2440238C3 (de) 1981-11-19
SU546277A3 (ru) 1977-02-05
DD120873A5 (ja) 1976-07-05
BE832684A (fr) 1976-02-23
CH599129A5 (ja) 1978-05-12
PL102294B1 (pl) 1979-03-31
FR2282423A1 (fr) 1976-03-19
BG26520A3 (ja) 1979-04-12
CS196286B2 (en) 1980-03-31
FR2282423B1 (ja) 1978-10-20
NL7509759A (nl) 1976-02-24
IT1041953B (it) 1980-01-10
CA1053704A (en) 1979-05-01
LU73223A1 (ja) 1977-04-15
JPS5143706A (ja) 1976-04-14
HU174007B (hu) 1979-10-28
RO69805A (ro) 1980-05-15
BR7505365A (pt) 1976-08-03
GB1526272A (en) 1978-09-27

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